Synthesis And Properties Of Asymmetric Porphyrins And Their Amino-acid Derivatives

Porphyrins and their relatives are the cores of chlorophyll molecules. As the primary electron donor, they participate in a series of important process in photosynthesis. So porphyrins are the significant compounds in artificial photosynthesis. In nature photosythesis, the substance conversion and energy storage are only macroscopical phenomena, but the formation of charge-separation state and electron transfer are the determinative factors. Therefore building model compounds to investigate on the intramolecular electron transfer and charge-separated state formation attracted considerable attention of scholar. In this dissertation, a series of PSâ…¡model compounds with porphyrins as photosensitizer were design and synthesis, and the intramolecular electron and energy transfer and charge-separated state formation were studied to make theory foundation for the further modeling of PSâ…¡.In the thesis, several asymmetrical porphyrins bearing hydroxyl group were synthesized by Adler method; two porphyrins bearing amino group were synthesized by nitration of TPP and TNP. Those compounds were characterized by IR, 1H NMR and MS.14 novel porphyrin-amino acid compounds were synthesized from porphyrin and amino acid through protection of amino group of amino acid with Fmoc-OSu, then activation of carboxyl group with SOCl2, and characterized by IR, 1H NMR and MS. The photoelectric properties of compounds were studied in detail to make foundation for the further synthesis of porphyrin-bipyridine-Mn model compounds containing amino acid moiety. In addition the reaction mechanism of compounds 6, 7, 8, 9, which synthesized through esterification and included two amino acid chains, was discussed.